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Publication numberUS4642201 A
Publication typeGrant
Application numberUS 06/770,158
Publication dateFeb 10, 1987
Filing dateAug 27, 1985
Priority dateAug 27, 1985
Fee statusLapsed
Also published asDE218080T1, DE3680739D1, EP0218080A1, EP0218080B1
Publication number06770158, 770158, US 4642201 A, US 4642201A, US-A-4642201, US4642201 A, US4642201A
InventorsFerdinand L. Vogel
Original AssigneeIntercal Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Compositions for improving the stability of intercalated graphite structural members
US 4642201 A
Abstract
Members, such as bearings, gaskets, electrical conductors and the like, as well as containing coatings, made from graphite intercalated with a metal halide exhibit superior stability except when used or stored in an extremely humid atmosphere. In a humid atmosphere these members and coatings tend to swell, crack and develop a corrosion layer over time. In accordance with the present invention, however, members and coatings made from intercalated graphite mixed with from 2 vol. % to about 30 vol. % of a metal powder do not exhibit this environmental instability.
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Claims(14)
What is claimed is:
1. A powder for forming an environmentally stable member, comprising:
a metal halide intercalated graphite; and
a metal selected from the group consisting of copper, nickel, silver, molybdenum and tungsten; wherein said metal comprises from about 2 volume percent to about 30 volume percent of said environmentally stable powder.
2. An environmentally stable intercalated graphite member comprising a compact body formed from:
a metal halide intercalated graphite; and
a finely divided metal powder selected from the group consisting of copper, nickel, silver, molybdenum and tungsten; wherein said finely divided metal powder comprises from about 2 volume percent to about 30 volume percent of said compact body.
3. An environmentally stable intercalated graphite coating comprising:
a metal halide intercalated graphite;
a finely divided metal powder selected from the group consisting of copper, nickel, molybdenum and tungsten; and
a liquid resin binder; wherein said metal powder comprises from about 2 volume percent to about 30 volume percent of said coating based on the total volume of the intercalated graphite and metal powder.
4. The powder in accordance with claim 1 wherein the metal is a finely divided metal powder.
5. The powder in acordance with claim 4 wherein the metal halide is selected from the group consisting of a halide of a transition element, a halide of a group III A, IV A, V A and VI A metal or metalloid.
6. The powder in accordance with claim 5 wherein the metal halide is selected from the group consisting of copper chloride, cobalt chloride, nickel chloride, chromium chloride, cadmium chloride and ferric chloride.
7. The member in accordance with claim 2 wherein the metal halide is selected from the group consisting of a halide of a transition element, a halide of a group III A, IV A, V A and VI A metal or metalloid.
8. The member in accordance with claim 2, wherein the member further comprises a polymer selected from the group of a thermoplastic and a thermosetting polymer.
9. The member in accordance with claim 2 further comprising ceramic powder.
10. A member in accordance with claim 2, wherein the member is a bearing.
11. A member in accordance with claim 2, wherein the member is a gasket.
12. A member in accordance with claim 2, wherein the member is an electric contact.
13. The coating in accordance with claim 3 wherein the metal halide is selected from the group consisting of halide of a transition element, a halide of a group III A, IV A, V A and VI A metal or metalloid.
14. The coating in accordance with claim 13 wherein the metal halide is selected from the group consisting of copper chloride, cobalt chloride, nickel chloride, chromium chloride, cadmium chloride and ferric chloride.
Description

This invention relates to compositions that improve the environmental stability of members and composites such as bearings, gaskets, electrical contacts, conductive and lubricating coatings, and the like, comprised of intercalated graphite.

BACKGROUND OF THE INVENTION

It has recently been discovered that intercalated graphite has characteristics such as high electrical conductivity, good lubricity and the ability to form strong, coherent bodies, thus making it ideally suited for formation into members such as gaskets, bearings, electrical contacts and the like or for use in conductive, self-lubricating coatings. Also, the electrically conducting and lubricating characteristics of intercalated graphite can be successfully applied by dispersing it in a matrix to form a composite.

In general, many intercalated graphites display superior stability in air and at elevated temperatures. However, certain intercalated graphite (i.e., those intercalated with the metal halides) tend to exhibit some environmental instability when used or stored under extremely high humidity. When members, composites or coatings formed from such intercalated graphites are exposed to extremely high humidity for an extended period, swelling and cracking takes place and a corrosion layer forms on the surface.

In addition, when certain of these intercalated graphite are mixed with polymer powders or resins (i.e., a thermoplastic or a thermoset), or ceramic powders and then formed into a structural member or coating, the member or coating will begin to exhibit salt-like growths on its surface when it is exposed to extremely high humidity.

It is, therefore, an object of the invention to provide a metal halide intercalated graphite powder which may be formed into a member or coating that does not exhibit corrosion upon exposure to a extremely damp atmosphere.

It is another object of this invention to provide metal halide intercalated graphite members and coatings which do not crack, swell, or corrode when exposed to high humidity.

Still another object of the invention is to provide a metal halide intercalated graphite/polymer, metal or ceramic composite that when formed into a suitable member will show resistance to corrosion.

SUMMARY OF THE INVENTION

According to the invention, these and other objects are achieved by forming the desired member or coating from a metal halide intercalated graphite that is mixed with a metal such as copper, nickel, silver, molybdenumm or tungsten.

The stable members of the present invention are formed from an intercalated graphite/metal powder mixture which may be compressed either uniaxially (i.e., a die or mold) or isostatically (i.e., in a pressurized fluid) to form a compact of the described shape and strength and is, in addition to the metal powders, the compact may contain metal reinforcement, polymer resins or powders, ceramic powders and even exfoliated graphite. The compact may already be in the desired form or alternatively may be milled in a lathe to the desired shape.

The stable coatings of the present invention are formed from a intercalcated graphite/metal powder mixture which is suspended in liquid resin binder and optionally a solvent. The coating is applied to a surface and cured in a manner known to those skilled in the art to form a hard environmental stable surface.

DETAILED DESCRIPTION OF THE INVENTION

Intercalated graphite has several properties which may be used advantageously in forming useful three dimensional members, as well as, in surface coatings. When graphite is intercalated, it exhibits certain metal-like properties including increased electrical conductivity, luster and ductility. Additionally, intercalated graphite, when compression molded, forms a coherent, strong three dimensional body. In contrast, non-intercalated graphite, when formed in a similar fashion, produces a body which is extremely weak and friable Furthermore, intercalated graphite exhibits improved self-lubricating properties.

These characteristics allow for intercalated graphite compositions which are suitable for use (when formed into the appropriate shape) as bearings, gaskets, electrical contacts (such as motor brushes, electro discharge tools, etc.), electrical conductors, conductive coatings and the like.

The intercalated graphite compounds suitable for use with the foregoing members are those which are stable in air. The intercalated compounds having this property include but are not limited to those intercalated with metal halides such as halides of the transition elements, halides of Group III A, IV A, V A and VI A metals or metalloids. The preferred Group III A metals and metalloids being Boron, Aluminum, Gallium and Indium.

Of these metal halides, the preferred intercalating species are copper chloride, nickel chloride, and chromium chloride.

After the graphite is intercalated, if a three dimensional member is desired, the intercalcated graphite is formed into the desired shape in a mold through the action of pressure and temperature either uniaxially, isostatically or using a combination of both.

In addition to intercalated graphite, the molded members may optionally include metal reinforcement, polymers, ceramic powders and the like.

If an intercalcated graphite coating is desired, the intercalcated graphite is suspended in a liquid binder and, optionally, a suitable solvent. The mixture is coated on a surface and cured to a hard self-lubricating, electrically conductive surface.

In general, the metal halide intercalated graphites are stable intercalated graphite compounds. However, members and coatings made from these intercalated graphites may suffer from environmental stability problems under certain conditions. Metal halide intercalated graphites used or stored in extremely damp air (i.e. 80% R.H. and above) for an extended period of time (30 to 90 days or more) begin to swell and crack. In addition, a corrosion layer may form on the surface of the member.

This problem, as it occurs in intercalated graphite members, appears to be a function of the temperature and pressure used to form the member, as well as, the type of graphite used. However, this problem is also seen in intercalated graphite containing coatings. Since these coatings are typically not prepared at elevated temperatures and pressure, the environmental insalibility problem seems to be mainly a funciton of the type of graphite used.

Table I, demonstrates this situation for a copper chloride intercalated graphite member stored in an atmosphere having a 80% R.H.

              TABLE I______________________________________Forming Pressure         Forming Temperature                        Time*(PSI)         (C.)   (DAYS)______________________________________10,000         20            >400 1,000        200            62115,000        20             550,000        200            30______________________________________ *For appearance of the corrosion, cracking, etc.

An alternative for alleviating this difficulty is to use low member forming pressures and temperatures and to use intercalated graphite members and structures under moderate to normal humidity applications or to limit the types of graphites to those which are known not to suffer from environmental instability. However, the lowering of the forming temperature and pressure leads to a comparable reduction in hardness and strength and thus, the humidty restriction would limit the applicability of the intercalated graphite members.

In accordance with the present invention, a metal halide intercalated graphite which is mixed with certain amounts of transition metals, such as nickel, copper, silver molybdenum or tungsten prior to the member forming step does not exhibit the environmental instability described above. These metals are preferrably used in powder form, however, the required metal content may alternatively be provided by electrodeposition of the metal onto the intercalated graphite or by reducing a metal halide mixed with the intercalated graphite to a metal.

The amount of metal powder mixed with the intercalated graphite may vary from about 2 vol. % to about 30 vol %. The amount used depends on forming temperature and pressure applied when the intercalated graphite/metal mixture is formed into a usable member. Table II indicates the amount of copper powder required to eliminate the instability of a member formed from copper chloride intercalated graphite.

              TABLE II______________________________________Forming Pressure       Forming Temperature(PSI)       (C.)    Vol. % Copper______________________________________100,000      20             2100,000     100             16100,000     200             30 10,000      20             2 10,000     100             2 10,000     200             2______________________________________

More than 30 vol % metal may be added if the application requires, however, 30 vol. % appears to be the maximum amount of metal needed to prevent the above described environmental instability.

The intercalated graphite/metal powder mixture may be mixed together in any known manner which produces a thoroughly mixed composition. For example, a vibrating mixer provides suitable results. The metal employed should be finely divided powder having a size of about 20 microns to about 100 microns.

After the mixing step is complete, the mixture may be formed into a suitable member using the methods described above.

If it is desired, the metal intercalated graphite mixture may further contain a thermosetting or a theromplastic polymer or a ceramic powder. In addition, the members formed from the metal intercalated/graphite mixture, may contain metal reinforcing and may even be encased in metal depending upon the use to which the particular member will be put.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4414142 *Nov 20, 1981Nov 8, 1983Vogel F LincolnOrganic matrix composites reinforced with intercalated graphite
US4565649 *Jul 30, 1984Jan 21, 1986Intercal CompanyGraphite intercalation compounds
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4795591 *Mar 18, 1988Jan 3, 1989Nippon Steel CorporationProcess for the preparation of graphite intercalation compound and novel graphite intercalation compound
US4798771 *Aug 27, 1985Jan 17, 1989Intercal CompanyFriction resistance
US4799956 *Feb 17, 1987Jan 24, 1989Intercal CompanyIntercalatd graphite gaskets and pressure seals
US4799957 *Feb 17, 1987Jan 24, 1989Intercal CompanyGraphite and metal or halide
US5260124 *Nov 25, 1991Nov 9, 1993The United States Of America As Represented By The Administrator Of The National Aeronautics And Space AdministrationIntercalated hybrid graphite fiber composite
US5371324 *Nov 24, 1992Dec 6, 1994Yazaki CorporationLightweight, noncorrosive and excellent electroconductivity; used for telephones, electrostatic copying machine, printers, electronic calculators, video tapes, and electronic ranges
US5376450 *Sep 30, 1992Dec 27, 1994Ucar Carbon Technology CorporationLow surface acid intercalated graphite and method
US5447681 *Dec 27, 1993Sep 5, 1995Mando CorporationWet mixing phenol or furfural resins with mixture of natural graphite, copper, molebdynum disulfide and lead, press molding and firing
US5499827 *Jun 30, 1993Mar 19, 1996Thermal Dynamics International, Inc.Seal for shafts and valve stems
US5609708 *Dec 11, 1995Mar 11, 1997Suggs; Steven M.Method of making a seal for shafts and valve stems
US5797982 *Jan 8, 1997Aug 25, 1998Acadia Elastomers CorporationApparatus for manufacturing a seamless packing material
US5902762 *Apr 4, 1997May 11, 1999Ucar Carbon Technology CorporationEmbedded needle-shaped ceramic fibers extending into the graphite sheet to increase the permeability to a liquid resin solution; used for making gaskets
US5972506 *May 6, 1996Oct 26, 1999Etienne Lacroix Tous Artifices S.A.A sodium potassium intermetallic carbides or a cyclic polymer, for use in lithium batteries; nontoxic, durability, readily industrialized, no violent reaction when it is immersed in water, moderate cost
US6037074 *Jul 7, 1998Mar 14, 2000Ucar Carbon Technology CorporationFlexible graphite composite for use in the form of a fuel cell flow field plate
US6060189 *Jun 3, 1998May 9, 2000Ucar Carbon Technology CorporationElectrically conductive seal for fuel cell elements
US6087034 *Jul 9, 1998Jul 11, 2000Ucar Graph-Tech Inc.Flexible graphite composite
US6254993Aug 13, 1998Jul 3, 2001Graftech Inc.Flexible graphite sheet with decreased anisotropy
US6432336 *Apr 12, 2000Aug 13, 2002Graftech Inc.Flexible graphite article and method of manufacture
US6433067Feb 5, 2001Aug 13, 2002Graftech Inc.Formable flexible graphite sealing composites
US6758881Mar 25, 2003Jul 6, 2004Tris Inc.Metal-graphite brush and production method thereof
US8163387 *Apr 25, 2008Apr 24, 2012Akebono Brake Industry Co., Ltd.Organic friction modifier comprising laminar graphite and aramid resin
USRE36206 *Aug 14, 1997May 4, 1999Indian Head IndustriesHeating to increase thickness and fill in gaps and imperfections; eliminates requirement for overtorquing head and exhaust gaskets
DE4234688A1 *Oct 14, 1992Apr 22, 1993Yazaki CorpVerfahren zur herstellung eines elektrisch leitenden verbundmaterials
EP1985885A1 Apr 24, 2008Oct 29, 2008Akebono Brake Industry Co., Ltd.Organic friction modifier
Classifications
U.S. Classification252/503, 252/511, 252/506
International ClassificationF16C33/12, F16C33/24, C10M111/04, H01H1/025, C09K3/10, C04B35/536, C10N10/02, C10N10/10, C10N50/08, B22F1/00, F16J15/10, C10N40/14, C10N10/08, C10N10/12, C10N10/16, C10N40/02, H01B1/06, H01H1/027, C10M103/00, C10N10/06, C04B30/00, H01B1/04, F16C33/16, H01H1/02, C01B31/00, F16J15/12
Cooperative ClassificationC04B35/536, H01B1/06, F16C33/16, H01H1/027, F16J15/102, F16J15/126, C01B31/0415
European ClassificationC01B31/04C, F16J15/12B6, F16C33/16, F16J15/10B, C04B35/536, H01H1/027, H01B1/06
Legal Events
DateCodeEventDescription
Apr 25, 1995FPExpired due to failure to pay maintenance fee
Effective date: 19950215
Feb 12, 1995LAPSLapse for failure to pay maintenance fees
Sep 20, 1994REMIMaintenance fee reminder mailed
Feb 8, 1991FPAYFee payment
Year of fee payment: 4
Feb 8, 1991SULPSurcharge for late payment
Sep 11, 1990REMIMaintenance fee reminder mailed
Nov 21, 1985ASAssignment
Owner name: INTERCAL COMPANY, 1600 WASHINGTON, PORT HURON, MI.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:VOGEL, FERDINAND L.;REEL/FRAME:004484/0376
Effective date: 19851111